Process for producing amino derivatives of hexahydrodiphenyl



Patented Mar. 29, 1932 OFFICE;

unner KOBTEN, or FRANKFORT-ON-THE-MAIN-FEOHENHEIM', GERMANY PROCESS FORK PRODUCING AMINO DERIVATIVES OF HEX-AHYDRODIPHENYL No Drawing. Application filed .Tune 14, 1930, Serial No. 461,257,

This application isa continuation in part of my application Serial N 0. 343,570, filed February 28, 1929. I

I have found, that the, three-nuclear con- '5 densation products which correspond probnaphthalene and 2.5 parts of a ably to the general formula: v IIIXz IIIXQ in which formula the Xs mean hydrogen or an alkylgroup and one or more hydrogen atoms of the aromatic nuclei as well as of the hydroaromatic residue may be substituted by an alkylor-alkoxygroup, are converted in one operation into aminoderivatives of hem-,- hydrophenyl by treating the three-nuclear products immediately with hydrogen 1n the presence of a base metal hydrogenation cat-- alyst, advantageously under su'peratmospheric pressure and with addition of astutable diluent. I V

The aminoderivatives thus obtained are identical with those formed according to the process described in the parent application.

In order to further illustrate my invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees; but I wish 1t tobe understood that my'invention is not limited to the examplesg ven,vnor to the exact conditions stated therein.:

Example, 1

50 parts of 4.4!-diamino 3.3=din1ethyl-di phenyl-cyclohexane, 50 parts of rdecahydrocatalyst, prepared by precipitatingrthe carbonates of nickel, cobalt, copper andbismuth on silica gel and reducing in: a hydrogen atmosphere" in the usual manner, are heated to 180 while well stirring under a hydrogen pressure of atmospheres. The absorption of hydrogen] occurs rather quickly. The reaction 1s 'fin- "ing at 1682170 1 am1no-3-methyl-1.-2C3.4'.5'.6'. 1.1-diphenyl thus produced in a retical It represents when hexane in about 100 controlled by the fact'that ver s e z and in Germany March 2, 1928.

taken up. By fractional distillation in Vac uo a colorless oil boil under a pressure of 13 mm. small amounts of lower boil-1 tions have passed over. The new 4- hexahydronearly theoyield corresponds probably to the foris obtained after ing frac mula H2 .Hz

Hz, H27

pure a transparent oil boil-I ing at 175177 under a pressure of 15 mm., solidifying below 0.

The process may be carried out likewise when usin nickel, reduced at about 500 and precipitated on fullers earth or silica-gel and heating the mixture under a hydrogen pressure of 10 atmospheres.

7 Example 2 In airopen vessel provided with a stirrer and inlet and delivery tubes for gas a solution of '50 parts of -4,4-diamino-diphenyl-cyclothalene is heated wi th addition of 3 partsof a catalyst under or dinary pressure at 130 180 while introducing a current of hydrogen, which advantageously circulates. A suitable catalyst is obtained for instance by ing a solution containing about 85% nickel, 15% copper and 5% cerium with sodium carbonate for about 5l0% of its weight.

The course of the reacti in a sample taken out from time to time, when dilutesulphuric acidrisladded, anincreasing amount ofthe sulphate of diphenyl is p massisseparated from the catalyst and the solvent is expelled from the solution by steam. the residue, fro chloric' salt, of 4-ainino the. formed 4-aminohexahydro- -hexahydrodiphenyl orresponding to one 1' g a catalyst containing about 20%,;70

parts of tetrahydronaph-1' precipitat on can be easily r re cipitated. The warm reaction The hydrochloric acid is added to m which'on cooling the hydro -I claim 1. A process for producing aminoderivatives of hexahydrodiphenyl which comprises treating three-nuclear condensation products coril'esponding probably to the general formu a:

wherein X means hydrogen or a methyl group, with hydrogen in the presence of a carbonate of a heavy metal acting as hydrogenation catalyst.

2. A process forproducing aminoderivatives ofihexahydrodiphenyl which comprises treating three-nuclear condensation products corresponding probably to the general formula:

, wherein X means hydrogen or a methyl group, with hydrogen under superatmospheric pressure in ate of a heavy metal acting as hydrogenation catalyst.

3. A process for, producing aminoderivatives of hexahydrodiphenyl which comprises treating three-nuclear condensation products cori'esponding probably to the general formu a:

HzN NH;

wherein X' means hydrogen or a methyl with hydrogen under superatmospheric pressure in the presence of acarbonate of a heavy metal acting as hydrogenation catalyst with addition of an inert diluent.

4. A process for producing 4-amino-1'-2'- 3'-4-5-6-hexahydro-1.l-diphenyl which comprises treating 4c.4-diamino diphenyl-' cyclohexane with hydrogen inthe presence with hydrogen the presence of a carbon of a carbonate of a heavy metal acting as hydrogenation catalyst.

V 5. A process for producing 4-amino-3- methyl-1-2-3-4-5-6'-hexahydr0 1.1 diphenyl which comprises treating by-diamino-3.3-dimethyl diphenyl cyclohexane under superatmospheric pressuretin thepresence of-a carbonate of a heavy metal acting as hydrogenation catalyst.

In testimony whereof, I afiix my signature.

"ERNST KORTEN. 

